CN102163760B - Method for separating and recovering lithium and cobalt from positive electrode material of lithium battery - Google Patents
Method for separating and recovering lithium and cobalt from positive electrode material of lithium battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 154
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 148
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 125
- 239000010941 cobalt Substances 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000007774 positive electrode material Substances 0.000 title abstract 2
- 239000000706 filtrate Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000011343 solid material Substances 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000000605 extraction Methods 0.000 claims description 26
- 239000002699 waste material Substances 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000005030 aluminium foil Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 10
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 238000013467 fragmentation Methods 0.000 claims description 7
- 238000006062 fragmentation reaction Methods 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 23
- 230000008901 benefit Effects 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000002386 leaching Methods 0.000 abstract description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 238000007127 saponification reaction Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 7
- 230000008030 elimination Effects 0.000 description 6
- 238000003379 elimination reaction Methods 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention provides a method for separating and recovering lithium and cobalt from a positive electrode material of a lithium battery. The method comprises the following: (1) a step of physical disassembly and alkaline leaching; (2) a step of roasting and washing, namely adding sulfate into a black solid material containing lithium cobalt oxide obtained in the step (1) in the weight ratio of the black solid material to the sulfate being 1:(0.8-1.2), mixing, roasting for 2 to 6 hours at a temperature of between 600 and 800 DEG C, cooling, adding a cleaning solution in terms of the ratio of solid to liquid being 1:(3-5) to wash, agitating for 1 to 2 hours at a temperature of between 60 and 80 DEG C and filtering to obtain Li<+>-containing filtrate and filter residue containing lithium and a small amount of cobalt; (3) a step of reducing and acid saluting; and (4) a step of extracting the cobalt to obtain pure Co2<+> solution. By the method, high recovery ratios of the metal lithium and the metal cobalt are achieved, the recovery ratio of the lithium is over 90 percent, the obtained lithium and the obtained cobalt have high purity, the content of the lithium mixed in the cobalt is greatly reduced, and the purity of the cobalt can reach over 99.5 percent. Therefore, the method has higher economic benefits and social benefits.
Description
Technical field
The present invention relates to the processing of non-ferrous metal in waste lithium cell, relate in particular to a kind of method that reclaims lithium and cobalt of separating from anode material of lithium battery.
Background technology
The plurality of advantages such as volume is little, lightweight, specific energy is high because having for lithium battery, recycle long and without memory, be widely used in the electronic products such as notebook computer, mobile phone, digital camera and VCD.
China is largest production state and the maximum consumption state of lithium battery.The life-span of lithium battery is generally 3 years, and annual superseded waste lithium cell is hundreds of millions of.Typical metal content in the waste lithium cell positive electrode is: Co:22.31%, Li:3.74%, Ni:0.4%, Al:9.78% and Cu:7.47%.
Wherein, metallic cobalt is important strategic material.Only 470,000 tons of the explored cobalt tenors of China, and be present in cobalt mineralss mainly with the association form.The complicated occurrence state of cobalt mineralss, grade is low, and extraction process complexity and the rate of recovery are low.Therefore, exploration separating and recovering gold from existing waste and old cobalt-containing materials belongs to cobalt and seems especially important.It is reported, the battery industry cobalt consumption of China in 2007 is 6000 tons, accounts for 48% of domestic cobalt consumption figure, and cobalt is heavy metal element, and the cobalt in waste lithium cell arbitrarily abandons and will environment be caused to great harm.Therefore, how from waste lithium cell separating and recovering gold belong to cobalt and become a hot issue merited attention.
In addition, lithium metal is one of important energy source material of industrial development.The current whole world just increases with the speed in every year 5～8% demand of lithium and compound thereof.Particularly along with new-energy automobile over the years, paid attention to gradually, promoted and become the inexorable trend that substitutes orthodox car, as the output of the dynamic lithium battery of new-energy automobile " heart ", also being entered the phase of increasing rapidly.Expect 2012, the annual production of new-energy automobile will reach 1,000,000, will drive the demand of 5.2 ten thousand tons of anode material of lithium battery.The life-span of considering lithium battery is limited, and after several years, these new-energy automobile lithium batteries will progress into and eliminate the date of retirement, if the lithium in its positive electrode is arbitrarily abandoned, will cause the great wasting of resources.
Visible, from anode material of lithium battery, separating and recovering cobalt and lithium have very important Social benefit and economic benefit.
At present, from waste lithium cell, separating and recovering gold belongs to the method for cobalt and lithium and is: valuable metal is comprised to cobalt, copper and lithium all become soluble-salt and dissolve leaching from lithium battery, pass through again extraction or chemical back-and-forth method separating metal cobalt from leachate, again the lithium remained in leachate is separated to recovery subsequently.
There is following problem in the method:
(1) extraction: with organic extractant (as P204 and P507 etc.) extract and separate cobalt and lithium, exist mixed phase to carry secretly and organic extractant can extract the problem of a small amount of lithium simultaneously, when preparing the cobalt product, can cause the lithium content of cobalt product the inside higher, greatly affect the cobalt product quality;
(2) the chemo-selective precipitation method: by carbonic hydroammonium or ammonium oxalate precipitate cobalt, then dinectly bruning or thermal reduction preparing product, the final cobalt product impurity content of the method is higher, this be due to: (1) cobalt acid lithium material leachate also contains the impurity such as aluminium, copper, manganese, iron except cobalt and lithium; (2) lithium also can some precipitation; And, for the recovery of lithium, generally adopt carbonate precipitation method, but the rate of recovery of lithium generally only has 60% left and right, and purity is lower.
To sum up, at present from waste lithium cell, the method for separating and recovering cobalt and lithium can not effectively be separated cobalt with lithium, often mixes lithium in the cobalt product and causes quality to reduce, and the while rate of recovery of lithium is lower.Especially the higher waste lithium cell for lithium content, this problem is more serious.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of method that reclaims lithium and cobalt of separating from anode material of lithium battery, and the method can guarantee that lithium and cobalt all have the higher rate of recovery and higher purity simultaneously.
The invention provides a kind of method that reclaims lithium and cobalt of separating from anode material of lithium battery, comprise the following steps:
(1) physics is disassembled with alkali and is soaked: by waste lithium cell electric discharge, carry out physics and disassemble and obtain the positive electrode that load on aluminium foil has cobalt acid lithium; Alkali soaks rear filtration, separates aluminium foil and obtains the black solid material containing cobalt acid lithium;
(2) roasting and washing: by the above-mentioned black solid material containing cobalt acid lithium, be 1: 0.8～1.2 to add sulfate by weight, mix, 600～800 ℃ of lower roastings 2～6 hours, after cooling, by solid-to-liquid ratio, be 1: 3～5 to add cleaning solution washing, under 60～80 ℃, stir 1～2 hour, filter, obtain containing Li
+filtrate and contain cobalt and the filter residue of a small amount of lithium;
(3) reduction and acid are molten: by the filter residue in step (2), by solid-to-liquid ratio, be 1: 6～10 to add the acid solution of 1.0～3.0mol/L, and add hydrogen peroxide or sodium sulfite, 50～80 ℃ of lower stirring reactions 2～4 hours, filter, obtain the filtrate of containing cobalt and a small amount of lithium;
(4) Extraction of Cobalt: get organic extractant, Extraction of Cobalt the filtrate made from step (3), obtain pure Co
2+solution.
Step of the present invention (1) is raw material for getting waste lithium cell, obtaining load after physics is disassembled has the positive electrode of cobalt acid lithium, carries out subsequently alkali and soaks and make metallic aluminium generation chemical reaction, and positive electrode is separated with aluminium foil thus, filter, get filter residue and be the black solid material containing cobalt acid lithium.Preferably, alkali soaks for being 1: 3～6 to add end water by described positive electrode by solid-to-liquid ratio, and regulating pH value was 13～14,60～85 ℃ of stirrings 0.5～2 hour.Alkali soaks can be selected sodium hydroxide solution to carry out alkali to soak.Filtrate can be used for, reclaimed aluminium oxide.
In step (2), add sulfating roasting can make the lithium in waste lithium cell change into water-soluble sulfate, and other metallic compounds such as cobalt and copper are substantially all water insoluble, thereby realized the separation of lithium.Sulfate can be the common sulfate such as magnesium sulfate, ammonium sulfate or calcium sulfate.Preferably, sulfate is magnesium sulfate or ammonium sulfate.
Li
+in the water-washing process of this step, washed out, the rate of washing out reaches more than 90%.Cleaning solution can be applicable to being used herein to the liquid of washing for pure water, running water or other.
Preferably, contain Li
+filtrate can after to remove impurity by means of precipitation and condensing crystallizing, reclaim lithium.Under the environment that is 10 left and right in the pH value, lithium hydroxide is dissolved in filtrate, and simultaneously, the impurity such as copper, manganese, iron form precipitation and separated.Lithium salt after washing is higher, processes and just can obtain highly purified lithium solution a little, after condensing crystallizing, can obtain highly purified lithium salts.The rate of recovery of lithium is up to more than 90%, and purity is 98%～98.5%.
Contain Li
+filtrate be colourless, the inside is not contained cobalt (content of cobalt can be controlled in 20mg/L following) substantially, so does not substantially lose cobalt in this step.
In step (3), add hydrogen peroxide or sodium sulfite to be leached after making trivalent cobalt in the cobalt acid group be reduced into divalence.Preferably, the concentration of hydrogen peroxide is 30%, and addition is 1～3 times of the middle filter residue of step (2) by liquid-solid ratio.Also preferably, to count in mass ratio be 1～2 times of filter residue in step (2) to the addition of sodium sulfite.The filter residue produced in this step can return to further roasting and washing in step (2).
Acid solution can be sulfuric acid, hydrochloric acid, nitric acid or perchloric acid.Preferably, acid solution is sulfuric acid.
In step (4), Extraction of Cobalt can be: after the filtrate in step (3) is gone back to adjust pH to 3.5～4.0, elimination precipitates on a small quantity, obtains filtrate.The sulfonated kerosene that the P204 extractant that is separately 20% by volume fraction and volume fraction are 80% mixes, sodium hydroxide solution or ammoniacal liquor saponification with 6～10mol/L, obtain the saponification organic liquor, wherein, the volume ratio of extractant solution and aqueous slkali is 10: 1～15: 1, and saponification rate is 50～75%.According to saponification organic liquor volume, with the filtrate volume ratio, be 2～4: 1,4～6 stage countercurrent extractions, the raffinate obtained reclaims lithium, the hydrochloric acid back extraction of 2～4mol/L for the load organic liquor obtained, load organic liquor volume and hydrochloric acid volume ratio are 3～6: 1,6～8 stage countercurrent back extractions, obtain the pure Co of 60～110g/L
2+solution.
The present invention can further include the synthetic cobalt product of step (5): by pure Co in step (4)
2+solution under agitation, by excess coefficient, being 1.3～2.0 to add the ammonium bicarbonate soln that concentration is 180～230g/L, is under 35～55 ℃, to react 1～3 hour in temperature, and endpoint pH is 6.8～7.2, get that supernatant is dried, fragmentation makes cobalt carbonate, described cobalt carbonate makes cobalt powder through hydrogen reducing.
The method that reclaims lithium and cobalt of separating from anode material of lithium battery provided by the invention has following beneficial effect:
(1) rationally recycle lithium metal and the cobalt in the waste lithium cell positive electrode, turn waste into wealth, realized the cycling and reutilization of limited resources;
(2) reduced or eliminated the harmful effect that the metallic cobalt in the waste lithium cell positive electrode produces environment;
(3) rate of recovery of lithium metal and cobalt improves greatly, particularly the rate of recovery of lithium is brought up to more than 90% by former 60%, and the lithium obtained and the purity of cobalt are high, particularly greatly reduce the content of the lithium mixed in cobalt, the purity of cobalt can reach more than 99.5%;
(4) reasonable easily row, can industrialization, has high economic benefit and social benefit.
The accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.Fig. 1 is schematic flow sheet of the present invention.
Embodiment mono-
A kind of method that reclaims lithium and cobalt of separating from anode material of lithium battery comprises the following steps:
(1) physics is disassembled with alkali and is soaked: by waste lithium cell electric discharge, carry out physics and disassemble and obtain the positive electrode that load on aluminium foil has cobalt acid lithium; By this positive electrode, by solid-to-liquid ratio, be to add sodium hydroxide solution at 1: 3, regulating endpoint pH is 13, at 70 ℃, stirs 0.5 hour, and alkali soaks simultaneously and stirred, and filters afterwards, separates aluminium foil and obtains the black solid material containing cobalt acid lithium;
(2) roasting and washing: take 50g black solid material and add 50g magnesium sulfate, mix, 800 ℃ of roastings 2 hours, the fired slags 54.2g obtained, be to add pure water at 1: 3 by solid-to-liquid ratio, under temperature 60 C, stirs 2 hours, filters, and obtains containing Li
+the wash water that concentration is 7.5g/L, and obtain filter residue 43.3g, wherein cobalt content 56.4%, lithium content 0.31%, and wash water condensing crystallizing after removal of impurities reclaims lithium;
(3) reduction and acid are molten: getting the filter residue in step (2), is the sulfuric acid that adds 1mol/L at 1: 8 by solid-to-liquid ratio, adds sodium sulfite 65g, 50 ℃ of reactions 4 hours, filters, and the filtrate cobalt content obtained is 22.53g/L, and lithium content is 0.43g/L;
(4) after the filtrate in step (3) is returned to adjust pH to 4.0, elimination precipitates on a small quantity, obtains filtrate.The sulfonated kerosene that the P204 extractant that is separately 20% by volume fraction and volume fraction are 80% mixes, sodium hydroxide solution saponification with 10mol/L, obtain the saponification organic liquor, wherein, the volume ratio of extractant solution and aqueous slkali is 12: 1, and saponification rate is 60%.According to saponification organic liquor volume: filtrate volume is 3: 1,5 stage countercurrents extractions, and the raffinate obtained reclaims lithium, the hydrochloric acid back extraction of 2mol/L for the load organic liquor obtained, load organic liquor volume: the hydrochloric acid volume is 6: 1, and 6 stage countercurrent back extractions obtain the pure Co of 66.5g/L
2+solution, in raffinate, cobalt content is 1.2mg/L;
(5) by pure cobalt liquor obtained above under agitation, add the ammonium bicarbonate soln that the concentration with respect to excessive 1.5 times of cobalt is 180g/L, under 40 ℃, reaction is 2 hours, terminal pH7.04, in supernatant, cobalt content is 8.4mg/L, after the fragmentation of cobalt carbonate drying, reduces, and obtains cobalt powder.
The present embodiment can reach 90.5% by the removal efficiency of roasting lithium, to the rate of recovery of cobalt, can reach 97%, and purity is 99.5%, and the rate of recovery of lithium reaches 90%, and purity is 98%.
Embodiment bis-
A kind of method that reclaims lithium and cobalt of separating from anode material of lithium battery comprises the following steps:
(1) physics is disassembled with alkali and is soaked: by waste lithium cell electric discharge, carry out physics and disassemble and obtain the positive electrode that load on aluminium foil has cobalt acid lithium; By this positive electrode, by solid-to-liquid ratio, be to add sodium hydroxide solution at 1: 4, regulating endpoint pH is 13, under 80 ℃, stirs 1 hour, and alkali soaks simultaneously and stirred, and filters afterwards, separates aluminium foil and obtains the black solid material containing cobalt acid lithium;
(2) roasting and washing: take 50g black solid material and add 50g ammonium sulfate, mix, 700 ℃ of roastings 3 hours, the fired slags 50.2g obtained, be to add running water at 1: 3 by solid-to-liquid ratio, under temperature 70 C, stirs 1 hour, filters, and obtains containing Li
+the wash water that concentration is 7.2g/L, and obtain filter residue 40.1g, wherein cobalt content 53.4%, lithium content 0.42%, and wash water condensing crystallizing after removal of impurities reclaims lithium;
(3) reduction and acid are molten: getting the filter residue in step (2), is the sulfuric acid that adds 2mol/L at 1: 8 by solid-to-liquid ratio, adds sodium sulfite 60g, 80 ℃ of reactions 2 hours, filters, and the filtrate cobalt content obtained is 20.19g/L, and lithium content is 0.49g/L;
(4) after the filtrate in step (3) is returned to adjust pH to 4.0, elimination precipitates on a small quantity, obtains filtrate.The sulfonated kerosene that the P204 extractant that is separately 20% by volume fraction and volume fraction are 80% mixes, ammonia spirit saponification with 10mol/L, obtain organic saponification liquor, wherein, the volume ratio of extractant solution and aqueous slkali is 15: 1, saponification rate is 65%, according to saponification organic liquor volume: filtrate volume is 2.5: 1,5 stage countercurrent extractions, the raffinate obtained reclaims lithium, the hydrochloric acid back extraction of 3mol/L for the load organic liquor obtained, and load organic liquor volume: the hydrochloric acid volume is 6: 1,6 stage countercurrent back extractions, obtain the pure Co of 79.5g/L
2+solution, in raffinate, cobalt content is 3.2mg/L;
(5) by pure cobalt liquor obtained above under agitation, add the ammonium bicarbonate soln that the concentration with respect to excessive 1.8 times of cobalt is 200g/L, under 40 ℃, reaction is 2 hours, terminal pH7.10, in supernatant, cobalt content is 7.5mg/L, after the fragmentation of cobalt carbonate drying, reduces, and obtains cobalt powder.
The present embodiment can reach 88.5% by the removal efficiency of roasting lithium, to the rate of recovery of cobalt, can reach 98%, and purity is 99.5%, and the rate of recovery of lithium reaches 90%, and purity is 98.5%.
Embodiment tri-
A kind of method that reclaims lithium and cobalt of separating from anode material of lithium battery comprises the following steps:
(1) physics is disassembled with alkali and is soaked: by waste lithium cell electric discharge, carry out physics and disassemble and obtain the positive electrode that load on aluminium foil has cobalt acid lithium; By this positive electrode, by solid-to-liquid ratio, be to add sodium hydroxide solution at 1: 5, regulating endpoint pH is 13, under 60 ℃, stirs 2 hours, and alkali soaks simultaneously and stirred, and filters afterwards, separates aluminium foil and obtains the black solid material containing cobalt acid lithium;
(2) roasting and washing: take 50g black solid material and add 40g ammonium sulfate, mix, 600 ℃ of roastings 6 hours, the fired slags 49.7g obtained, be to add pure water at 1: 3 by solid-to-liquid ratio, at 75 ℃ of temperature, stirs 1 hour, filters, and obtains containing Li
+the wash water that concentration is 8.1g/L, and obtain filter residue 42.5g, wherein cobalt content 52.1%, lithium content 0.42%, and wash water condensing crystallizing after removal of impurities reclaims lithium;
(3) reduction and acid are molten: getting the filter residue in step (2), is the sulfuric acid that adds 3mol/L at 1: 6 by solid-to-liquid ratio, adds the hydrogen peroxide 80mL that concentration is 30%, 80 ℃ of reactions 2 hours, filter, the filtrate cobalt content obtained is 25.31g/L, and lithium content is 0.39g/L;
(4) after the filtrate in step (3) is returned to adjust pH to 3.5, elimination precipitates on a small quantity, obtains filtrate.The sulfonated kerosene that the P204 extractant that is separately 20% by volume fraction and volume fraction are 80% mixes, sodium hydroxide solution saponification with 10mol/L, obtain organic saponification liquor, wherein, the volume ratio of extractant solution and aqueous slkali is 10: 1, saponification rate is 50%, according to saponification organic liquor volume: filtrate volume is 4: 1,5 stage countercurrent extractions, the raffinate obtained reclaims lithium, the hydrochloric acid back extraction of 2mol/L for the load organic liquor obtained, and load organic liquor volume: the hydrochloric acid volume is 6: 1,6 stage countercurrent back extractions, obtain the pure Co of 60.3g/L
2+solution, in raffinate, cobalt content is 2.5mg/L;
(5) by pure cobalt liquor obtained above under agitation, add the ammonium bicarbonate soln that the concentration with respect to excessive 1.5 times of cobalt is 230g/L, under 50 ℃, reaction is 2 hours, terminal pH6.98, in supernatant, cobalt content is 14.2mg/L, after the fragmentation of cobalt carbonate drying, reduces, and obtains cobalt powder.
The present embodiment can reach 90.3% by the removal efficiency of roasting lithium, to the rate of recovery of cobalt, can reach 97%, and purity is 99.5%, and the rate of recovery of lithium reaches 90%, and purity is 98.5%.
Embodiment tetra-
A kind of method that reclaims lithium and cobalt of separating from anode material of lithium battery comprises the following steps:
(1) physics is disassembled with alkali and is soaked: by waste lithium cell electric discharge, carry out physics and disassemble and obtain the positive electrode that load on aluminium foil has cobalt acid lithium; By this positive electrode, by solid-to-liquid ratio, be to add sodium hydroxide solution at 1: 5, regulating endpoint pH is 13, under 60 ℃, stirs 2 hours, and alkali soaks simultaneously and stirred, and filters afterwards, separates aluminium foil and obtains the black solid material containing cobalt acid lithium;
(2) roasting and washing: take 50g black solid material and add 60g magnesium sulfate, mix, 600 ℃ of roastings 2 hours, the fired slags 55.2g obtained, be to add pure water at 1: 3 by solid-to-liquid ratio, at 75 ℃ of temperature, stirs 1 hour, filters, and obtains containing Li
+the wash water that concentration is 7.5g/L, and obtain filter residue 53.1g, wherein cobalt content 48.1%, lithium content 0.75%, and wash water condensing crystallizing after removal of impurities reclaims lithium;
(3) reduction and acid are molten: getting the filter residue in step (2), is the sulfuric acid that adds 3mol/L at 1: 8 by solid-to-liquid ratio, adds the hydrogen peroxide 70mL that concentration is 30%, 80 ℃ of reactions 2 hours, filter, the filtrate cobalt content obtained is 20.31g/L, and lithium content is 0.53g/L;
(4) after the filtrate in step (3) is returned to adjust pH to 4.0, elimination precipitates on a small quantity, obtains filtrate.The sulfonated kerosene that the P204 extractant that is separately 20% by volume fraction and volume fraction are 80% mixes, and the ammonia spirit saponification with 10mol/L, obtain the saponification organic liquor, and wherein, the volume ratio of extractant solution and aqueous slkali is 10: 1, and saponification rate is 75%.According to saponification organic liquor volume: filtrate volume is 2: 1,5 stage countercurrents extractions, and the raffinate obtained reclaims lithium, the hydrochloric acid back extraction of 3mol/L for the load organic liquor obtained, load organic liquor volume: the hydrochloric acid volume is 6: 1, and 8 stage countercurrent back extractions obtain the pure Co of 83.5g/L
2+solution;
(5) by pure cobalt liquor obtained above under agitation, add the ammonium bicarbonate soln that concentration that the cobalt excess coefficient is 1.6 is 200g/L, temperature is 55 ℃, and endpoint pH is 7.2, make cobalt carbonate through washing, oven dry, fragmentation, through hydrogen reducing, make cobalt powder.Obtain cobalt powder.
The present embodiment can reach 82.1% by the removal efficiency of roasting lithium, to the rate of recovery of cobalt, can reach 98%, and purity is 99.5%, and the rate of recovery of lithium reaches 90%, and purity is 98.5%.
Embodiment five
A kind of method that reclaims lithium and cobalt of separating from anode material of lithium battery comprises the following steps:
(1) physics is disassembled with alkali and is soaked: by waste lithium cell electric discharge, carry out physics and disassemble and obtain the positive electrode that load on aluminium foil has cobalt acid lithium; By this positive electrode, by solid-to-liquid ratio, be to add sodium hydroxide solution at 1: 6, regulating endpoint pH is 14, under 60 ℃, stirs 1 hour, and alkali soaks simultaneously and stirred, and filters afterwards, separates aluminium foil and obtains the black solid material containing cobalt acid lithium;
(2) roasting and washing: take 50g black solid material and add 60g magnesium sulfate, mix, 800 ℃ of roastings 6 hours, the fired slags 49.3g obtained, be to add pure water at 1: 5 by solid-to-liquid ratio, at 80 ℃ of temperature, stirs 1 hour, filters, and obtains containing Li
+the wash water that concentration is 9.5g/L, and obtain filter residue 48.1g, wherein cobalt content 55.7%, and lithium content 0.29% washings condensing crystallizing after removal of impurities reclaims lithium;
(3) reduction and acid are molten: getting the filter residue in step (2), is the sulfuric acid that adds 3mol/L at 1: 10 by solid-to-liquid ratio, adds the hydrogen peroxide 70mL that concentration is 30%, 80 ℃ of reactions 2 hours, filter, the filtrate cobalt content obtained is 21.84g/L, and lithium content is 0.27g/L;
(4) after the filtrate in step (3) is returned to adjust pH to 3.5, elimination precipitates on a small quantity, obtain filtrate, the sulfonated kerosene that the P204 extractant that is 20% by volume fraction and volume fraction are 80% mixes, sodium hydroxide solution saponification with 6mol/L, obtain the saponification organic liquor, wherein, the volume ratio of extractant solution and aqueous slkali is 15: 1, saponification rate is 50%, according to saponification organic liquor volume: filtrate volume is 3: 1, 4 stage countercurrent extractions, the raffinate obtained reclaims lithium, the hydrochloric acid back extraction of 2mol/L for the load organic liquor obtained, load organic liquor volume: the hydrochloric acid volume is 4: 1, 6 stage countercurrent back extractions, obtain the pure Co of 60g/L
2+solution,
(5) by pure cobalt liquor obtained above under agitation, add the ammonium bicarbonate soln that concentration that the cobalt excess coefficient is 1.6 is 200g/L, temperature is 35 ℃, endpoint pH is 7.1, make cobalt carbonate through washing, oven dry, fragmentation, described cobalt carbonate makes cobalt powder through hydrogen reducing, obtains cobalt powder.
The present embodiment can reach 92.4% by the removal efficiency of roasting lithium, to the rate of recovery of cobalt, can reach 97%, and purity is 99.5%, and the rate of recovery of lithium reaches 92%, and purity is 98.5%.
The method of lithium and cobalt is reclaimed in the separation from anode material of lithium battery that embodiment provides, and have following beneficial effect: (1) rationally recycles lithium metal and the cobalt in the waste lithium cell positive electrode, turns waste into wealth, and has realized the cycling and reutilization of limited resources; (2) reduced or eliminated the harmful effect that the metallic cobalt in the waste lithium cell positive electrode produces environment; (3) rate of recovery of lithium metal and cobalt improves greatly, particularly the rate of recovery of lithium is brought up to more than 90% by former 60%, and the lithium obtained and the purity of cobalt are high, particularly greatly reduce the content of the lithium mixed in cobalt, the purity of cobalt can reach more than 99.5%; (4) reasonable easily row, can industrialization, has high economic benefit and social benefit.
Claims (6)
1. one kind is separated the method that reclaims lithium and cobalt from anode material of lithium battery, it is characterized in that, comprises the following steps:
(1) physics is disassembled with alkali and is soaked: by waste lithium cell electric discharge, carry out physics and disassemble and obtain the positive electrode that load on aluminium foil has cobalt acid lithium; Alkali soaks rear filtration, separates aluminium foil and obtains the black solid material containing cobalt acid lithium;
(2) roasting and washing: the described black solid material containing cobalt acid lithium, by weight for 1:0.8 ~ 1.2, adding sulfate, is mixed, 600 ~ 800 ℃ of lower roastings 2 ~ 6 hours, after cooling, by solid-to-liquid ratio, be that 1:3 ~ 5 add the cleaning solution washing, stir under 60 ~ 80 ℃ 1 ~ 2 hour, filter, obtain containing Li
+filtrate and contain cobalt and the filter residue of a small amount of lithium;
(3) reduction and acid are molten: by the described filter residue in described step (2), by solid-to-liquid ratio, be the acid solution that 1:6 ~ 10 add 1.0 ~ 3.0mol/L, and add hydrogen peroxide or sodium sulfite, 50 ~ 80 ℃ of lower stirring reactions 2 ~ 4 hours, filter, obtain the filtrate of containing cobalt and a small amount of lithium;
(4) Extraction of Cobalt: get organic extractant, Extraction of Cobalt the described filtrate made from described step (3), obtain pure Co
2+solution.
2. the method for claim 1, is characterized in that, described in described step (2), sulfate is magnesium sulfate or ammonium sulfate.
3. the method for claim 1, is characterized in that, described step contains Li described in (2)
+filtrate can after to remove impurity by means of precipitation and condensing crystallizing, reclaim lithium.
4. the method for claim 1, is characterized in that, described in described step (3), the concentration of hydrogen peroxide is 30%, and addition is 1 ~ 3 times of the middle filter residue of step (2) by liquid-solid ratio.
5. the method for claim 1, is characterized in that, it is 1 ~ 2 times of filter residue in step (2) that the addition of sodium sulfite described in described step (3) is counted in mass ratio.
6. the method for claim 1, is characterized in that, further comprises that step (5) synthesizes the cobalt product: by pure Co described in described step (4)
2+solution under agitation, by excess coefficient, being 1.3 ~ 2.0 to add the ammonium bicarbonate soln that concentration is 180 ~ 230g/L, is under 35 ~ 55 ℃, to react 1 ~ 3 hour in temperature, and endpoint pH is 6.8 ~ 7.2, get that supernatant is dried, fragmentation makes cobalt carbonate, described cobalt carbonate makes cobalt powder through hydrogen reducing.
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